Method for manufacturing dielectric ceramic powder, and multilayer ceramic capacitor obtained by using the ceramic powder

ABSTRACT

The invention relates to a method for manufacturing dielectric ceramic powder and a multilayer ceramic capacitor using the ceramic powder. According to the invention, BaCO 3  powder is dispersed into a solution of solvent and dispersant to prepare BaCO 3  slurry and then the resultant BaCO 3  slurry is wet-milled. Also, TiO 2  powder slurry is mixed into the wet-milled BaCO 3  slurry to form mixed slurry and then the mixed slurry is dried into mixed powder. Finally, the dried mixed powder is calcined to produce BaTiO 3  powder.

CLAIM OF PRIORITY

This application claims the benefit of Korean Patent Application No. 2005-25891 filed on Mar. 29, 2005, in the Korean Intellectual Property Office, the disclosure of which is incorporated herein by reference.

BACKGROUND OF THE INVENTION

1. Field of the Invention

The present invention relates to a method for manufacturing dielectric ceramic powder. More particularly, the present invention relates to a method for manufacturing dielectric ceramic powder by using wet-milled BaCO₃ as raw powder to prepare raw ceramic powder via solid state reaction, thereby ensuring fine particle size and uniform particle size distribution, and a multilayer ceramic capacitor made from the ceramic powder.

2. Description of the Related Art

The information society of the 21st century has seen an increasing trend of digitalization, high-performance and high-reliability and multimedia in products such as electronic appliances, PC, HHP which chiefly utilize Multilayer Ceramic Capacitor (MLCC), one of the necessary passive devices of the electronics industry. Accordingly, MLCC parts have undergone higher-capacity and minimization fast. But this requires sheet lamination and fine BaTiO₃ particles having uniform size distribution as the dielectric power used. Also, tetragonality indicated by a c/a ratio of c-axis to a-axis of BaTiO₃ powder crystal needs to be higher(more than 1.008).

BaTiO₃ powder has been produced by hydrothermal synthesis, alkoxide method, solid state reaction and the like.

In hydrothermal synthesis, jel-type titanium hydrate is added to a great quantity of barium hydroxide to react at a high temperature of about 150° C. and under a high atmospheric pressure of 10, thereby producing crystalline BaTiO₃. This method has the advantage of directly producing spherical crystal BaTiO₃ sized about 100 nm but has the disadvantage of difficult design and maintenance of a reactor, and expensive manufacturing cost. Furthermore, recently, BaTiO₃ powder produced by hydrothermal synthesis has revealed significant defects such as oxygen vacancy and barium vacancy, which develop into pores in the case of heat treatment, thus deteriorating properties of BaTiO₃ powder.

Meanwhile in synthesizing BaTiO₃via hydrolysis of metal alkoxide, metal alkoaxide alcohol solution and Ba (OH) aqueous solution are mixed in a tube-type static mixer to react at a temperature of 80° C. This method is advantageous due to following reasons. Liquid phase employed herein as starting material is more reactive than solid jel-type titanium hydrate used in hydrothermal synthesis. This allows synthesizing at a relatively low temperature, and easy adjustment of the synthesized powder particle size to about 20 to 100 nm. However this method has drawbacks in that a synthesis device is hard to configure, and alkoxide reagent used as starting material is expensive. Furthermore, material cost is expensive due to use of alcohol solvent, and complicated process conditions such as synthesis temperature hamper mass productions.

Therefore, to manufacture low-priced BaTiO₃, solid state reaction is most advantageous. In solid state reaction, BaCO₃ powder and TiO₂ powder are used as starting powder. The BaCO₃ powder and TiO₂ powder are mixed, and then undergo solid phase reaction in a calcination process to be synthesized into final BaTiO₃ powder. To achieve lamination of dielectric layers, dielectric material powder should have small particle size and uniform particle distribution. But BaTiO₃ manufactured by solid state reaction reportedly does not exhibit uniform particle size distribution compared to BTO manufactured via other methods described above. In the end, in sold state reaction, one of essential factors for obtaining final uniform BaTiO₃ powder concerns uniform dispersion of BaCO₃ powder and TiO₂ powder in the early stage. Such technologies have been consistently developed.

For example, conventional technologies are disclosed in Korean Patent Application Publication Nos. 2002-0053749 and 2004-0038747. The Patent Application No. 2002-0053749 discloses barium titanate powder obtained by mixing barium compound and titanium dioxide having rutile ratio of up to 30% and BET specific surface area of at least 5 m²/g and calcining the same. Meanwhile, the Patent Application No. 2004-38747 teaches a technology of absorbing organic polymer compound into barium carbonate powder. According to inventions disclosed in the aforesaid patent application publications, advantageously, barium compound and titanium dioxide are mixed uniformly to enhance the degree of mixing. However despite dispersion of each element, the acicular shape of barium compounds remains unchanged, leading to inevitable contact among barium compounds due to their morphological properties. Consequently, there is a limit in obtaining optimal degree of mixing with titanium dioxide.

Another conventional technology is disclosed in Korean Patent Application Publication No. 2004-0020252. Herein, BaCO₃ powder is dry-milled spherically, mixed with TiO₂ powder, and then calcined. However according to the aforesaid technology, disadvantageously, such dry-milling does not reduce the number of BaCO₃ particles, and high stress placed on BaCO₃ does not disperse BaCO₃ particles properly, thus leading to agglomeration. Large specific surface area of powder, or small particle size results in uniform dispersion, but BaCO₃ according to the aforesaid technology does not diminish particle numbers, rendering uniform mixing with TiO₂ difficult. Thus, BaTiO₃ powder finally obtained agglomerates heavily among primary particles and forms secondary particles relatively bigger than primary particles, also causing uneven particle distribution of powder. BaTiO₃ powder with such properties may be hardly dispersible when applied to the MLCC, and unsuitable for the dielectric ceramic use for up to 1 μm lamination to ensure a high-capacity capacitor.

SUMMARY OF THE INVENTION

The present invention has been made to solve the foregoing problems of the prior art and it is therefore an object of the present invention to provide dielectric ceramic powder having fine particles and uniform particle size distribution, and high tetragonal crystalinity.

It is another object of the invention to provide a multilayer ceramic capacitor obtained by using the dielectric ceramic powder.

The invention will be explained hereunder.

As identified above, solid state reaction is the most economical method for producing BaTiO₃ powder having fine particles and uniform particle size, and high tetragonality to manufacture a high-capacity MLCC.

In solid state reaction, fine BaTiO₃ powder may be produced via BaCO₃ powder and TiO₂ powder having big specific surface area. But the acicular shape of BaCO₃ powder obstructs uniform mixing with TiO₂ powder even in the case of mechanical mixing via beads mill equipment, and renders it difficult to obtain uniform BaTiO3 powder after final calcination. Further, despite uniform dispersion of fine BaCO₃ and TiO2 powders, BaCO₃ power particles grow easily in the calcination process. Therefore the BaCO₃ powder particles grow even before reacting with TiO₂ and reaching a temperature at which BaTiO₃ particles are formed, thus making uniform reaction with TiO₂ difficult.

This increases unevenness of particles in case where fine BaTiO₃ powder is produced via solid state reaction to laminate dielectric layers.

Therefore, the inventors have conducted studies and experiments to solve problems of the solid state reaction. As a result, they confirmed that fine particles of BaCO₃ powder could be obtained effectively by wet-milling acicular-shaped BaCO₃ raw powder into a slurry and changing the particle shape from acicular to spherical. Also, the inventors found that fine BaTiO₃ powder with high tetragonality and uniform particle size distribution could be produced by mixing TiO₂ powder having a big specific surface area into such fine and spherical BaCO₃ slurry, drying and cacinating the mixed slurry.

According to an aspect of the invention for realizing the object, there is provided a method for manufacturing dielectric ceramic powder comprising steps of:

dispersing BaCO₃ powder into a solution of solvent and dispersant to prepare a slurry and then wet-milling the slurry;

mixing TiO₂ powder slurry into the wet-milled BaCO₃ slurry to form mixed slurry and then drying the mixed slurry into mixed powder; and

calcining the dried mixed powder to produce BaTiO₃ powder.

According to another aspect of the invention for realizing the object, there is provided a method for manufacturing dielectric ceramic powder comprising steps of:

dispersing BaCO₃ powder into a solution of solvent and dispersant to prepare a slurry and then wet-milling the slurry;

mixing CaCO₃ powder slurry and TiO₂ powder slurry into the wet-milled BaCO₃ slurry to form mixed slurry, and then drying the mixed slurry; and

calcining the dried mixed powder to produce BaCaTiO₃ powder.

According to further another aspect of the invention for realizing the object, there is provided a multilayer ceramic capacitor comprising:

a multilayer ceramic structure having a plurality of dielectric layers and a plurality of internal electrodes alternating with the dielectric layers; and

external electrodes provided at both ends of the multilayer ceramic, electrically connected to at least one of the internal electrodes,

wherein the dielectric layers comprise the dielectric ceramic powder manufactured according to the methods.

BRIEF DESCRIPTION OF THE DRAWINGS

The above and other objects, features and other advantages of the present invention will be more clearly understood from the following detailed description taken in conjunction with the accompanying drawings, in which:

FIG. 1 illustrates a process for producing dielectric ceramic powder of the invention;

FIG. 2 a is a graph illustrating particle size change in accordance with wet-milling duration of the invention;

FIG. 2 b is a graph illustrating effects of ammonia addition on viscosity of BaCO₃ slurry in a wet-milling process of the invention;

FIG. 3 is a sectional view illustrating a multilayer ceramic capacitor manufactured via the dielectric ceramic powder of the invention;

FIG. 4a is SEM picture of BaCO₃ powder before wet milling;

FIG. 4 b is SEM picture of BaCO₃ powder wet-milled according to the invention;

FIG. 5 a is FE-SEM picture illustrating mixed powder of BaCO₃ powder and TiO₂ powder obtained without wet milling;

FIG. 5 b is FE-SEM picture illustrating mixed powder of BaCO₃ powder wet-milled according to the invention and TiO₂ powder;

FIG. 6 a is FE-SEM picture of the mixed powder of FIG. 5 a which was heat-treated at a temperature of 900° C.;

FIG. 6b is FE-SEM picture of the mixed powder of FIG. 5 b which was heat-treated at a temperature of 900° C.;

FIG. 7 a is FE-SEM picture illustrating morphology of BaTiO₃ powder manufactured according to a conventional solid state reaction;

FIG. 7 b is a graph illustrating particle size distribution of BaTiO₃ powder of FIG. 7 a;

FIG. 8 a is FE-SEM picture illustrating an example of morphology of BaTiO₃ powder produced according to the invention;

FIG. 8 b is a graph illustrating particle size distribution of BaTiO₃ powder of FIG. 8 a;

FIG. 9 a is FE-SEM picture illustrating another example of morphology of BaTiO₃ powder obtained according to the invention;

FIG. 9 b is a graph illustrating particle size distribution of BaTiO₃ powder of FIG. 9 a.

DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENT

Preferred embodiments of the present invention will now be described in detail with reference to the accompanying drawings.

FIG. 1 illustrates a process for manufacturing dielectric ceramic powder of the invention. As shown in FIG. 1, according to the invention, first, BaCO₃ powder is dispersed into a solution of solvent and dispersant to prepare BaCO₃ slurry. The dispersant, e.g. polyacrylic dispersant, is added to increase dispersibility of powder. Preferably, the dispersant is added to 1-5 weight parts with respect to BaCO₃ raw powder. The BaCO₃ raw powder is acicular, and preferably should have a specific surface area of 5 to 30 m²/g by BET measurement.

Further, according to the invention, distilled water and alcohol may be used as the solvent, but distilled water is preferable.

More preferably, the BaCO₃ powder is dispersed into the solution to such an extent that that the BaCO₃ slurry contains 10 to 60 wt % BaCO₃. Less than 10 wt % BaCO₃ out of the BaCO₃ slurry adversely affects productivity (mass productivity). Also, BaCO₃ in excess of 60 wt % out of the BaCO₃ slurry degrades dispersibility and impairs wet milling.

Then, according to the invention, the BaCO₃ slurry is wet-milled. The wet-milling is carried out at a speed of 1800 rpm via beads mill type equipment that uses zirconia beads with a diameter of 0.3 mm. Preferably, the milling duration should be limited to up to 20 hours. More preferably, the BaCO₃ powder is wet-milled so as to have a specific surface area of at least 30 m²/g by BET measurement.

With increase in milling time for BaCO₃ slurry, particle size of BaCO₃ powder decreases, leading to continuous increase in the specific surface area thereof. But as shown in FIG. 2( a), the specific surface area does not increase any more after 8 hours, increasing viscosity of slurry significantly. However, increased viscosity renders continuous wet-milling process difficult and thus it is necessary to reduce viscosity.

Therefore, according to the invention, to reduce viscosity of slurry, as shown in FIG. 2( b), ammonia should be preferably added in the wet-milling process. More preferably, the ammonia can be added to at least 0.1 wt % with respect to the solvent.

Then, according to the invention, TiO₂ powder slurry is mixed into the wet-milled BaCO₃ slurry to form mixed slurry. TiO₂ slurry can be easily manufactured by dispersing TiO₂ powder into a solution of solvent and dispersant. The TiO₂ raw powder preferably have a specific surface area of at least 20 m²/g, and more preferably at least 45 m²/g.

At this time, to produce BaTiO₃ powder in a following process, TiO₂ powder is mixed into a slurry to such an extent that a Ba/Ti mole ratio becomes 1. In this mixing process, the BaCO₃ slurry and TiO₂ slurry can be wet-mixed via zirconia beads with a diameter of 0.3 mm.

Meanwhile, sheet lamination of a high-capacity MLCC increases induced electric field, resultantly deteriorating IR and TCC properties. Therefore, to solve this problem, if necessary, TiO₂ slurry and CaCO₃ slurry as well may be mixed into the wet-milled BaCO₃ slurry. With such mixing of CaCO₃ slurry, Ca-doped BaTiO₃, or fine BaCaTiO₃ powder can be obtained in a following process.

Thereafter, the mixed slurry is dried to produce dried mixed powder, preferably, at a temperature of up to 200° C. The invention is not limited to the aforesaid drying method but spray drying method may be more preferable.

Also, if necessary, the dried powder may be coarsely crushed via atomizer.

And the dried mixed powder is calcined to synthesize dielectric ceramic powder such as BaTiO₃ powder or BaCaTiO₃ powder. In a calcination process, BaCO₃ powder and TiO₂ powder may undergo solid state reaction to form BaTiO₃ dielectric powder. Further, in case where CaCO₃ powder is additionally mixed, Ca-doped BaCaTiO₃ power can be obtained. Preferably, the calciantion temperature ranges from 900 to 1100° C.

Powders synthesized in this fashion have necking among primary particles. To be used for the MLCC, typically, the mixed powders could go through a process of separation from primary particles undamaged. To this end, according to the invention, the synthesized ceramic powder can be pulverized. The pulverizing process can be carried out effectively through deagglomeration in beads mill.

Typical solid state reaction is applied to the dielectric ceramic powder manufactured according to the aforesaid process. Still the dielectric ceramic powder may have uniform particle size distribution, with mean particle size of 150 nm to 250 nm, D10/D50 of at least 0.6 and D90/D50 of up to 1.4. based on FE-SEM picture

Also, the dielectric ceramic powder may have at least 5.0 m₂/g of BET specific surface area, and based on FE-SEM picture, a c/a ratio of c-axis to a-axis of the powder crystal lattice is at least 1.009.

Meanwhile, organic binder, solvent and other additives may be mixed with the dielectric ceramic powder obtained to prepare ceramic slurry, and a dielectric layer for the MLCC, or green sheets may be manufactured by using the ceramic slurry via a general tape casting method. Y₂O₃, Mn₃O₄, Cr₂O₃ and glass are used as additives.

FIG. 3 is a sectional view illustrating a multilayer ceramic capacitor manufactured via the dielectric ceramic powder. As shown in FIG. 3, the multilayer ceramic capacitor (MLCC) 10 includes a multilayer ceramic structure having a plurality of dielectric layers 1 and a plurality of internal electrodes 3 alternating with the dielectric layers; and external electrodes 5 provided at both ends of the multilayer ceramic structure.

To manufacture the capacitor 10, first, ceramic slurry including the dielectric ceramic powder prepared as described above is used to form the dielectric layers 1 through the typical tape casting method. Then the internal electrodes 3 are formed on the dielectric layers 1 via screen printing. Subsequently firing is carried our for the multilayer ceramic structure including the unfired dielectric layers 1, and then applying a conductive paste on both ends of the multilayer ceramic structure and finally firing it, thereby producing the multilayer ceramic capacitor 10 having the external electrodes 5.

As described above, according to the invention, to uniformly disperse and mix BaCO₃ powder and TiO₂ powder, before mixing with TiO₂ powder, only acicular-shaped BaCO₃ powder is wet-milled to be made spherical. Spherical particle shape or significant reduction in particle size allows uniform mixing with TiO₂ Also, dielectric ceramic powder having fine particle size of 150 to 250 nm and high tetragonality can be manufactured by reacting BaCO₃ powder with TiO₂ powder before BaCO₃ powder particles grow in a calcination process.

Further, in case where the multilayer ceramic capacitor is manufactured via the dielectric ceramic powder produced by the aforesaid process, sheet lamination is ensured to effectively realize higher-capacity of the MLCC while reducing the size thereof.

The invention will be explained in detail with reference to the unlimited examples which follow.

EXAMPLE 1

BaCO₃ raw powder having a specific surface area of20 m²/g was prepared. Some of BaCO₃ raw powder was dispersed into a mixed solution of distilled water and polyacrylic dispersant to manufacture BaCO₃ slurry. BaCO₃ raw powder was dispersed into the solution to such an extent that the BaCO₃ slurry would contain 10 to 60wt % BaCO₃ The slurry was wet-milled for 18 hours via beads mill type equipment that uses zirconia beads with a diameter of 0.3 mm as milling media. During wet-milling, considering a sudden increase in viscosity in accordance with decrease in BaCO₃ particle numbers, ammonia was added after 8 hour milling to reduce viscosity. A specific surface area of the wet-milled BaCO₃ powder was 31 m²/g, a significant increase from the initial one, and the particles had almost a spherical shape.

Field Emission (FE-SEM) picture before and after wet-milling BaCO₃ is shown in FIG. 4( a-b). As shown in the aforesaid FIG. 4( a-b), wet-milling changed BaCO₃ from acicular powder into finer spherical powder.

Meanwhile, slurried TiO₂ powder having a specific surface area of 45 m²/g was mixed into the wet-milled BaCO₃ slurry, and then the mixed slurry was mixed via beads mill. At this time, mixed powder was slurried so that BaTiO₃ powder would have a Ba/Ti ratio of 1. Then for comparison, BaCO₃ raw powder, which was not wet-milled, was mixed with TiO₂ powder to produce mixed powder.

FIG. 5( a-b) shows FE-SEM picture of the final mixed powder. FIG. 5( a) is FE-SEM picture illustrating BaCO₃ powder mixed with TiO₂ powder without wet-milling, while FIG. 5( b) is FE-SEM picture of wet-milled BaCO₃ powder mixed with TiO₂ power. As shown in FIG. 5( a-b), when BaCO₃ powder without wet-milling was mixed with TiO₂ powder, it leads to uneven mixing but use of the wet-crushed BaCO₃ powder led to uniform mixing among each component.

Also, to confirm whether BaCO₃ powder particles grow in case of rising temperature during a calcination process, mixed powders prepared as above were calcined and heat-treated at a temperature ranging from 600° C. to 1000° C. Consequently, as in FIG. 6( a), in case of using BaCO₃ powder without wet-milling, BaCO₃ particles grew considerably at a temperature of 900° C., while as in FIG. 6( b), in case where wet-milled BaCO₃ powder was used, particle growth was not observed, indicating that BaTiO₃ powder can be synthesized.

EXAMPLE 2

TABLE 1 Specific surface area Wet-milling of (m²/g) Calcination No. BaCO₃ BaCO₃ TiO₂ CaCO₃ temp. (° C.) 1 Not wet-milled 20 20 1020 2 Not wet-milled 20 20 1040 3 Wet-milled 31 20 1020 4 Wet-milled 31 20 1040 5 Wet-milled 31 45 960 6 Wet-milled 31 45 990 7 Wet-milled 31 45 1020 8 Wet-milled 31 45 30 960 9 Wet-milled 31 45 30 990

BaCO₃ raw powder having a specific surface area of 20 m²/g was prepared. Some of BaCO₃ raw powder was dispersed into a mixed solution of distilled water and polyarcrylic dispersant to produce BaCO₃ slurry. BaCO₃ powder was dispersed into the solution to such an extent that BaCO₃ slurry would contain 10 to 60 wt % BaCO₃. The resultant slurry was wet milled for 18 hours via beads mill type equipment using zirconia beads with a diameter of 0.3 mm as milling media. Considering a sudden increase in viscosity in accordance with decrease in BaCO₃ particle numbers during a wet-milling process, ammonia was added to reduce viscosity after 8-hour milling. A specific surface area of the wet-milled BaCO₃ powder is shown in Table 1 above.

Slurried TiO₂ raw powder having different specific surface area was mixed into the wet-milled BaCO₃ slurry via beads mill. The mixed powder was slurried so that BaTiO₃ powder would have a Ba/Ti ratio of 1, and then the mixed powder was obtained by spray drying.

Meanwhile, in manufacturing Ca-doped BaCaTiO₃ dielectric ceramic powder, as shown in Table 1, slurried TiO₂ powder and slurried CaCO₃ powder having a specific surface area of 30 m²/g were mixed into the wet-milled BaCO₃. At this time, to obtain (Ba_(0.98)Ca_(0.02))_(1.000)TiO₃ powder, each of TiO₂ powder and CaCO₃ powder were mixed into a slurry form, and then dried by spraying dying to produce mixed powder.

For comparison, as shown in Table 1, some of BaCO₃ raw powder having a specific surface area of 20 m²/g was wet-mixed with TiO₂ powder having a specific surface area of 20 m²/g without undergoing wet-milling. The powders were measured and mixed so that resultant BaTiO₃ powder would have a Ba/Ti ratio of 1.

The resultant mixed powders were dried and calcined under the conditions set forth in Table 1 to manufacture BaTiO₃ or BaCaTiO₃ dielectric ceramic powder. Thereafter, the ceramic powder was deagglomerated via beads mill to produce final powder.

To examine properties of powders manufactured as above, BET specific surface area was measured. Also, through XRD analysis, a c/a ratio of c-axis to a-axis of the powder crystal lattice was calculated to measure tetragonality, and the results are shown in Table 2 below. Mean particle size (D_(mean)) of powder was measured via image analyzer based on FE-SEM picture. Further, to investigate uniformity of particle size distribution, measurement was conducted on 10% cumulative distribution D10, 50% cumulative distribution D50, and 90% cumulative distribution D90, respectively from small size distribution. The calculated results of D10/D50, D90/D50 are shown in Table 2.

TABLE 2 Particle size Ceramic SSA* MPS* distribution Tetrago- No. powder (m²/g) (nm) D10/D50 D90/D50 nality 1 BaTiO₃ 5.66 176 0.41 1.57 1.0070 2 BaTiO₃ 3.97 212 0.40 1.54 1.0097 3 BaTiO₃ 4.58 199 0.62 1.38 1.0097 4 BaTiO₃ 4.01 230 0.65 1.36 1.0103 5 BaTiO₃ 5.68 150 0.70 1.26 1.0093 6 BaTiO₃ 4.53 202 0.69 1.24 1.0105 7 BaTiO₃ 4.08 218 0.72 1.24 1.0105 8 BaCaTiO₃ 5.62 155 0.71 1.27 1.0091 9 BaCaTiO₃ 4.57 198 0.70 1.24 1.0103 *SSA: Specific Surface Area *MPS: Mean Particle Size

As shown in Tables 1 and 2, for sample 1 in which BaCO₃ was calcined at a temperature of 1020° C. without wet-milling, the particles were finely-sized with 176 nm but tetragonality thereof was 1.007, which is lower than 1.008 or a requirement for high-capacity dielectric powder. For sample 2 in which BaCO₃ was calcined at a temperature of 1040° C., BaTiO₃ having tetragonality of 1.0097 and size of about 212 nm was synthesized.

In contrast, for sample 3, in which BaCO₃ was wet-milled and then mixed with 20 m²/g of TiO₂, BaCO₃ particles were finely-sized with 199 nm and tetragonality thereof was 1.0097, a high figure even at a temperature of 1020° C., which is lower than when BaCO₃ was not wet-milled. Also, for sample 6 in which BaCO₃ was wet-milled and then mixed with TiO₂ powder having a specific area of 45 m²/g, BaTiO₃ powder particles were sized 202 nm, with tetragonality of at least 1.010 at a temperature of 990° C. Further, for sample 5 in which BaCO₃ was calcined at a temperature of 960° C., BaCO₃ powder was obtained with fine particle size of 150 nm and big specific surface area of 5.68 m²/g. Still, BaTiO₃ powder obtained had high tetragonality of 1.0093.

In addition, to compare particle uniformity based on cumulative particle size distribution, the calculated values of D10/D50, D90/D50 were considered. Herein, bigger D10/D50 value and smaller D90/D50 value mean more uniform distribution. When the calculated values are compared, wet-milled BaCO₃ indicates bigger D10/D50 and smaller D90/D50, and thus more uniform particle size distribution than that without wet-milling. For mixed powders (samples 5 to 7) in which wet-milled BaCO₃ was mixed with TiO₂ having a specific surface area of 45 m²/g, the particle size distributions were most uniform.

Further, Ca-added BaCaTiO₃ powder (samples 8 to 9) exhibited behavior similar to BaTiO₃ powder. By calcining at a temperature of 990° C. and 960° C., BaCaTiO₃ powders having mean particle size of 198 nm and 155 nm, respectively, could be produced with tetragonality of at least 1.0091 overall.

FIGS. 7 a, 8 a and 9 a are FE-SEM pictures of dielectric ceramic powder corresponding to samples 2, 3 and 6. FIGS. 7 b, 8 b and 9 b are graphs illustrating particle size distribution measured via image analyzer. As shown in the above FIGS. 7 a, 7 b, 8 b and 9 b, compared to sample 2 which used BaCO₃ without wet-milling, sample 3 which used wet-milled BaCO₃ powder indicated more uniform particle size distribution. Further, the narrowest particle size distribution was found in sample 6 which used wet-milled BaCO₃ powder and TiO₂ powder having big specific surface area.

As set forth above, according to the invention, BaTiO₃ or BaCaTiO₃ is manufactured via wet-milled BaCO₃ powder to produce uniform dielectric ceramic powder having fine particles sized 150 to 250 nm and high tetragonality.

Also, the multilayer ceramic capacitor manufactured via dielectric ceramic powder allows sheet lamination and enables higher-capacity and minimization of the MLCC.

While the present invention has been shown and described in connection with the preferred embodiments, it will be apparent to those skilled in the art that modifications and variations can be made without departing from the spirit and scope of the invention as defined by the appended claims. 

1-26. (canceled)
 27. A multilayer ceramic capacitor comprising: a multilayer ceramic structure having a plurality of dielectric layers and a plurality of internal electrodes alternating with the dielectric layers; and external electrodes provided at both ends of the multilayer ceramic, electrically connected to at least one of the internal electrodes, wherein the dielectric layers comprise the dielectric ceramic powder manufactured by dispersing BaCO₃ powder into a solution of solvent and dispersant to prepare a slurry and then wet-milling the slurry; mixing TiO₂ powder slurry into the wet-milled BaCO₃ slurry to form mixed slurry and then drying the mixed slurry into mixed powder; and calcining the dried mixed powder to produce BaTiO₃ powder.
 28. The multilayer ceramic capacitor according to claim 27, wherein the ceramic power has uniform particle size distribution, with mean particle size of 150 nm to 250 nm, D10/D50 of at least 0.6 and D90/D50 of up to 1.4 based on FE-SEM picture.
 29. The multilayer capacitor according to claim 27, wherein the ceramic powder has at least 5.0 m₂/g of BET specific surface area, and based on FE-SEM picture, a c/a ratio of c-axis to a-axis of the powder crystal lattice is at least 1.009. 